Contamination of dairy products with tris(2,4-di-tert-butylphenyl) phosphite and implications for human exposure.

Tris(2,4-di-tert-butylphenyl) phosphite (AO168), an organophosphite antioxidant, can be oxidized to tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O) during the production, processing, and application of plastics. AO168 = O can be further transformed to bis(2,4-di-tert-butylphenyl) phosphate and 2,4-di-tert-butylphenol. Here, we discovered the contamination of AO168 and its transformation products in dairy products for the first time. More samples contained AO168 (mean concentration: 8.78 ng/g wet weight [ww]), bis(2,4-di-tert-butylphenyl) phosphate (mean:11.1 ng/g ww) and 2,4-di-tert-butylphenol (mean: 46.8 ng/g ww) than AO168 = O (mean: 40.2 ng/g ww). The concentrations of AO168 and its transformation products were significantly correlated, and differed with the packaging material and storage conditions of the product. Estimated daily intakes (EDIs) of AO168 and its transformation products were calculated. Although the overall dietary risks were below one, transformation products accounted for 96.7% of the total hazard quotients. The high-exposure EDIs of total AO168 were above the threshold of toxicological concern (300 ng/kg bw/day), and deserve continual monitoring.

Simultaneous determination of 9 environmental pollutants including bisphenol A in vegetable oil by solid phase extraction-liquid chromatography-tandem mass spectrometry.

In this study, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method with solid phase extraction was established for the simultaneous determination of bisphenol A, bisphenol F, bisphenol S, 4-nonylphenol, n-nonylphenol, octylphenol, n-octylphenol, perfluorooctane sulfonate acid and perfluorooctanoic acid in vegetable oil. The sample was extracted with ammonia acetonitrile solution (1 : 9, V/V) by ultrasonication. And the obtained extract was purified by using a PRIME HLB solid phase extraction column. The identification and quantification of the compounds was performed by liquid chromatography-tandem mass spectrometry in multiple reaction monitoring (MRM) mode. The internal standard method was used for quantitative analysis. Under optimal experimental conditions, the limits of quantitation of bisphenol A, bisphenol F, bisphenol S, 4-nonylphenol, n-nonylphenol, octylphenol and n-octylphenol in vegetable oil were 1.0 µg kg-1. The limits of quantitation of perfluorooctane sulfonic acid and perfluorooctanoic acid in vegetable oil were 0.1 µg kg-1. The average spiked recoveries of the method were in the range of 89.2-117.1% with the relative standard deviations (RSD) of 2.9-9.8% (n = 6). This method is sensitive, versatile and reproducible, and is suitable for the simultaneous determination of bisphenol A, bisphenol F, bisphenol S, 4-nonylphenol, n-nonylphenol, octylphenol, n-octylphenol, perfluorooctane sulfonate acid and perfluorooctanoic acid in vegetable oil.

Ultra-performance liquid chromatography tandem mass spectrometry for the rapid simultaneous analysis of nine organophosphate esters in milk powder.

Organophosphate esters (OPEs) are common flame retardants that are used in a wide variety of products. These compounds might migrate into and pollute food products. An analytical method involving an improved approach called the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) was developed to simultaneously measure trace levels of nine OPEs in milk powder. Separation of the nine OPEs was optimized on a reversed-phase column within 7 min. The stable isotope tri-n-butyl phosphate-d27 (TBP-d27) was used as an internal standard. This method was validated in terms of its linearity, sensitivity, precision, accuracy and matrix effects. Matrix-matched calibration curves were constructed with 1/x(2) as the weighting factor for all of the target compounds resulting in coefficients of regression lines between 0.9938 and 0.9999. The average accuracy was between 73.5% and 110.2%. Intra- and inter-assay precisions for six replicates ranged from 3.9% to 8.9% or below 11%, respectively. The limits of detection (LODs) were in the range of 0.1-0.25 µg/kg, and the limits of quantification (LOQs) were below 1.5 µg/kg. Significant matrix effects have been observed, but suppression or enhancement of the signal was compensated for by the use of an isotopically labeled internal standard. This validated method was successfully applied to determine the concentrations of the OPEs in milk powder.